JPS5845401B2 - hair dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention utilizes a melanin precursor substance or a similar substance to the hair, and applies a water-soluble salt of a highly safe metal to the hair. This involves a highly safe permanent hair dye that can be dyed under mild conditions, and compared to previous attempts of this kind,
The aim is to obtain an excellent black hair dye.

Currently, the basic and frequently used permanent hair dyeing technology is to oxidize azo dyes, which are mainly made of aromatic amines such as para-phenylene diamine and their derivatives, with hydrogen peroxide in the presence of an alkali. It polymerizes and penetrates into the hair keratin.

However, it is well known that paraphenylenediamine-based oxidized hair dyes, which are the main type of hair dyes, have the risk of causing allergic reactions, and the treatment conditions are not alkaline. Because of this, there is also concern about primary irritation.

In the past, attempts have been made to dye hair using natural melanin precursors such as tyrosine and β-(3,4-dihydroxyphenyl)alanine (Dopa) to solve this problem, but they are not strong enough. The conditions for obtaining good dyeing have not been found and the method has not been successful.

The present inventors have been conducting research on natural hair dyeing using these melanin precursors, and have previously used highly hydrophilic substances such as dithiothreitol and dithioerythreitol as cystine bond-breaking agents. It was discovered that the use of tyrosine and dopa in addition to tyrosine and dopa in the reaction system facilitates the subsequent melanin production reaction and provides good dyeing properties without inhibiting the enzymatic reaction. Then, 5-hydroxyindole, methyl 5,6-cyhydroxyindole-2-carboxylate, etc. are added as an effect promoter,
They discovered that a hair dye could be obtained by using tyrosinase and/or persulfate in the oxidation process, and filed a patent application.

(% Kaisho 5O-88240) Subsequently, the present inventors have attempted to dye hair using melanin precursors or similar substances in order to further improve the dyeing power, and as a result, sulfites or Bisulfites or their effect promoters include ethylene carbonate, propylene carbonate, γ
- By a pretreatment agent containing one or more of butyrolactone, γ-valerolactone, δ-valerolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, or a derivative thereof. Hair is treated in advance and melanin precursors or similar substances such as pyrocatechol, β-(3,4-dihydroxyphenyl)alanine (dopa), dopamine, 6-hydroxydopamine, 5,6-cyhydroxyindole 2-carvone are added to the hair. Methyl acid, 1-(3,4-dihydroxyphenyl)-
2-aminoethanol, (3,4-dihydroxyphenyl)-2-(methylamino)ethanol, homocatechol, Ptert-butylcatechol, 3,4-dihydroxybenzaldehyde, 2,3-dihydroxybenzoic acid, 3,4- Dihydroxybenzoic acid, caffeic acid, pyrogallol, gallic acid, methyl gallate, ethyl gallate, propyl gallate, isopropyl gallate, 2.4
・5-) IJ Hydroxytoluene, ■・2-dihydroxyphenyl, 2,3 dihydroxynaphthalene, 5-hydroxyindole, which is an 0-dihydroxy compound or a monohydroxy compound selected from the group of purpurogalin, is used as a substrate to prepare iron or copper. We have discovered that hair can be dyed black (black or a tone close to black) under extremely mild conditions by applying hydrogen peroxide in the presence of a water-soluble salt.

Among these precursors, pyrocatechol, for example, belongs to what is called a modifier in the field of ordinary oxidative hair dyes, and is used for the purpose of changing the color tone in this type of hair dye. It is clear from Table 1, FIGS. 1 and 2 (A1) that it is impossible to dye the hair black.

Some hair dyeing techniques that are considered to be related to this type of hair dyeing involve tannic acid, etc., acting on iron salts, but most of them are dyed by treating the hair with mercaptan, etc., in advance under alkaline conditions, which is unpleasant. It is accompanied by an odor, and the texture of the finished hair is not necessarily satisfactory.

The hair dye of the present invention has a natural black finish (black or a tone close to black) and also imparts a desirable texture to the hair.

When dyeing hair, the above-mentioned sulfite or hydrogen sulfite, or one or two of the above-mentioned auxiliary substances such as ethylene carbonate, propylene carbonate, γ-butyrolactone, β-methyl-γ-butyrolactone, and derivatives thereof, are added in advance. Hair is pre-treated with a pre-treatment agent containing a compound selected from the above, and 0.00% water-soluble copper salt or iron salt is added to the hair.
01-1.0 mol (liquid), preferably 0105-0.2
It is recommended that the metal salts be thoroughly adsorbed and penetrated into the hair by treatment with mole (liquid), and that the metal salts attached to the outside of the hair be removed. These are conditions for efficient pigment production using metal salts.

At this time, the appropriate concentration of hydrogen peroxide is 0.5 to 3%.

In this way, the hair dye of the present invention has a pH value of
It is highly safe because it can be performed with a 100% water treatment, and it also provides a highly durable and permanent dye.

Next, the evaluation results of the hair dye obtained according to the present invention will be described.

(1) Apply 10 gr of the above formula to a hair sample washed and dried under certain conditions at 2 gr as a hair dye pre-treatment agent.
After processing at 0°C for 10 minutes, wash with water and wipe off.

[Pre-treatment liquid]

Ammonium bisulfide 150% (70
%) Aqueous solution ethylene carbonate 15.0 Furopylene carbonate 10.0 Ethyl alcohol 15.0 Purified water
45.0 total 100.0% pH = 6.5 (2) Next, the treated hair was immersed in 10 gr of each 0.2 mol (liquid) copper salt or iron salt aqueous solution (pH = 4 to 6). , at 30°C for 10 minutes, and then gently wiped off.

(3) Apply the following precursor solution (pH 3,
5-5.0) Apply 10 gr evenly to the hair,
Dip and dye at 30°C for 10 minutes.

[Previous, precursor solution]

Precursor (0.1 mol (liquid) equivalent to 1.0-2.2%) Ethyl alcohol 20.0 Hydrogen peroxide solution (30%) 3.33 Purified water
74.47~75.67 total 100.00
% After dyeing, rinse with shampoo and dry in the usual way.

(4) The dyed hair was visually evaluated for dye density and color tone by five panelists (Table 1).

Furthermore, the color was measured using a spectrophotometer (Hitachi 607 Color Analyzer) and converted to Hunter's (L, a, b, c,), which determined the brightness of the dyed hair (L value) (Figure 1).
The hue and saturation (a, b, c values) (Figure 2) in the (a, b) plane were evaluated.

That is, according to Table 1 and Figure 1, the new catechol-based hair dye (Tsuta 5.6) of our invention, which uses a metal salt selected from copper and iron, is simply an ammonia-based hair dye for catechol. Hair dyeing using conventional technology that involves oxidative polymerization (
1) or without any pretreatment (2.
3) and when done without hydrogen peroxide (Tsuta 4)
) shows superior dyeability compared to

Also, O-dihydroxy compounds containing catechol (molecular weight 1
10-220) (厘5.6.10.11.12.13.
It can be seen that 5-hydroxyindoles of 14, 15, 16, 17) and 18) and A19 also exhibit excellent dyeing properties.

A7.8 and 9 seem to have slightly inferior dyeability when judged only by the L value, but the saturation C is low and visually gives sufficient black or near-black dyeability. .

On the other hand, m-dihydroxybenzene (A20121), which is excluded from the scope of our invention, and a compound in which one hydroxyl group is methoxylated (A, 22) have large values for both L value and chroma, and have poor dyeability. I understand that

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 (1) Pretreatment liquid ammonium bisulfite solution 15.0% (70%
%) Imidazole-based amphoteric surfactant Lauric acid jetanolamide Ethyl alcohol Ethylene carbonate Purified water 15.0 1.5 10, O 15.0 43.5 Total 100.0% (2) Allow the metal salt liquid to pass through, Removal of metal salts adhering to the outside of the hair is a condition for efficient pigment production by the subsequently applied pigment precursor and metal salt.

At this time, the appropriate concentration of hydrogen peroxide is 0.5 to 3%.

In this way, the hair dye of the present invention has a pH value of
It is highly safe because it can be performed with a 100% water treatment, and it also provides a highly durable and permanent dye.

Next, the evaluation results of the hair dye obtained according to the present invention will be described.

(1) Apply 10 gr of the above formula to a hair sample washed and dried under certain conditions at 2 gr as a hair dye pre-treatment agent.
After processing at 0°C for 10 minutes, wash with water and wipe off.

[Pre-treatment liquid]

Ammonium bisulfide 15.0% (7
0%) Aqueous solution ethylene carbonate 15.0 Propylene carbonate 10.0 Ethyl alcohol 15.0 Purified water
45.0 total 100.0% pH - 6,5 (2) Next, the treated hair was immersed in 10 gr of each 0.2 mol (liquid) copper salt or iron salt aqueous solution (pH - = 4 to 6). Then, treat it at 30℃ for 10 minutes, and wipe it off.

(3) Apply the following precursor solution (pH-3) to the hair.
, 5-5.0) Apply 10g evenly to the hair,
Dip and dye at 0°C for 10 minutes.

[Precursor solution]

Precursor (equivalent to 0.1 mol (liquid) 1.0-2.2%) Ethyl alcohol 20. O Hydrogen peroxide solution (30%) 3.33 Purified water
74.47~75.67 total 100.0
0% After dyeing, rinse with shampoo and dry in the usual way.

(4) The dyed hair was visually evaluated for dye density and color tone by five panelists (Table 1).

Furthermore, the color was measured using a spectrophotometer (Hitachi 607 Color Analyzer) and converted to Hunter's (I,, a, b, c,), which determined the brightness of the dyed hair (L value) (Figure 1).
, and (a, b) hue and saturation in the plane (a, b, c
(Figure 2) was evaluated.

That is, according to Table 1 and Figure 1, the new catechol-based hair dye (Tsuta 5.6) of our invention, which uses a metal salt selected from copper and iron, is simply an ammonia-based hair dye for catechol. Hair dyeing using conventional technology that involves oxidative polymerization (
A1) or without any pretreatment (B2.
3) and when done without hydrogen peroxide (Tsuta 4)
) shows superior dyeability compared to

Also, 0-dihydroxy compounds containing catechol (molecular weight 1
10-220) (A5.6.10, 11.12.1
3.14.15.16.17, and 18) and 應1
It can be seen that 5-hydroxyindole No. 9 also exhibits excellent dyeing properties.

A7.8 and 9 seem to have slightly inferior dyeability when judged only by the L value, but the saturation C is low and visually gives sufficient black or near-black dyeability. .

On the other hand, m-dihydroxybenzene (Arashi 20.21), which is excluded from the scope of our invention, and a compound in which one hydroxyl group is methoxylated (A, 22) have large values for both L value and chroma, and are difficult to dye. I understand that I am inferior.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 (1) Pretreatment liquid ammonium bisulfite solution $15.0% (7
0%) Imidazole amphoteric surfactant Lauric acid jetanolamide Ethyl alcohol Ethylene carbonate Purified water 15, 0 1, 5 10, 0 15, 0 43, 5 Total 100.0% (2) Metal salt liquid Propylene carbonate Isoprobil Alcohol polyoxyethylene purified water total 10% 0 3 100% (2) Metal salt solution Ferrous sulfate L-ascorbic acid 2.2% 0.1 Oleyl alcohol ethylene oxide (10 mol) adduct 5.0 Purified water 92. 7 Total 00.0% (3) Precursor solution Pyrocatechol DL-dopa L-ascorbate hydroethyl cellulose isostearyl alcohol ethylene oxide (10 mol) adduct 1.2% 0.8 0.2 0.2 4. 0 Purified water 93.6 Total ■ 00.0% (4) Oxidizing agent solution Hydrogen peroxide solution (30%) 25.0% Stabilizer Appropriate amount of purified water
75.0 Total 100.0% Hair is treated with 80 gr of pre-treatment liquid (1) for 10 minutes and then washed with water.

Next, 80 gr of metal salt solution (2) was applied, left to stand for 10 minutes, and excess solution was gently wiped off.

Then, the precursor solution (3): oxidizer solution (4) was mixed into 4:
A permanent black hair dye is obtained by applying 80 gr of the solution mixed in a ratio of 1:1 to the entire hair and leaving it for 15 minutes.

Example 4 (1) Pretreatment liquid Ammonium bisulfite aqueous solution (70%) sodium sulfite ethylene carbonate γ-butyrolactone Ethyl alcohol hydroxyethyl cellulose Flopylene glycol purified water 10.0% 5.0 15.0 5.0 5.0 0.5 3.0 56.5 Total ioo, o% (2) Metal salt solution cupric acetate polyoxyethylene polyoxyb Ropyrene copolymer lauryl alcohol polyoxye Tyrene (6 mol) adduct purified water 2.0% 2.0 3.0 95.0 Total 100.0% (3) Precursor solution Pyrocatechol 5-hydroxyindole 5,6-cyhydroxyin Methyl 2-carboxylate L-ascorbic acid Doll Ethyl alcohol hydroxyethyl cellulose lauryl alcohol polyoxye Tyrene (6 mol) adduct purified water 1.0% 0.5 0.5 0.2 15.0 1.0 3.0 78.8 (4) Oxidizing agent solution Hydrogen peroxide solution (30%) stabilizer purified water Total 100.0% 15.0% Appropriate amount 85.0 Total 100.0% Hydrogen peroxide solution (30%) stabilizer purified water 15.0% Appropriate amount 85.0 Total 100.0 By the same treatment as in Example 6 Get your hair dyed.

Example 9 (1) Pretreatment liquid, dark brown permanent ammonium bisulfite solution (70%) Ethylene carbonate γ-valerolactone α-methyl-γ-butyrolactone Purified water meter (2) Metal salt liquid Glycine Steel purified water 15 .0% 10.0 5.0 5.0 65.0 100.0 1.0% 99.0 Total 100.0 (3) Precursor solution Seven-pyrocatechol 1.0% Hydroxydopamine 0.5 2 ・4・ 5 Entries Hydroxytolyl 0.1 3,4-dihydroxybenzoic acid 0.12,3-
Dihydroxybenzoic acid 0.1 Ammonia water (2
8%) Appropriate amount of purified water
98.2 Total 100.0 (4) Oxidizing agent liquid Hydrogen peroxide solution (30%) 18.0% Stabilizer Appropriate amount of purified water
82.0 Total 100.0 First, hair was treated with a pretreatment solution (1180gr) for 10 minutes, and then washed with water.

Next, apply 80 gr of metal salt solution (2) to the hair for 10
After letting it stand for a minute, gently wipe off excess liquid.

Then, the precursor solution (3):oxidant solution (4) was mixed in a ratio of 4:1.
A permanent black hair dye is obtained by applying 80 gr of the mixed solution to the entire hair and leaving it for 15 minutes.

Hydrogen peroxide solution (30%) 18.0% stabilizer Appropriate amount of purified water
82.0 total 100.0 First, hair was treated with a pretreatment solution (1180gr) for 10 minutes, and then washed with water.

Next, apply 80 gr of metal salt solution (2) to the hair for 10
After letting it stand for a minute, gently wipe off excess liquid.

Then, mix the precursor solution (3) and the dioxide solution (4) in a ratio of 4:1.
After applying 80 gr of the mixed solution to the entire hair, leave it for 15 minutes to obtain permanent black hair dye.

Example 7 (1) Pretreatment liquid Sodium sulfite 1.5% Ammonium bisulfite solution 10.0 (70%) Propylene carbonate δ-valerolactone β-methyl-γ-butyrolac Purified water 5.0 1.0 tons 1, 0 81.5 Total 100.0 (2) Metal salt solution Glycine Copper Hydroxyethyl Cellulose Purified water Total (3) Precursor solution Pyrocatechol 1-(3,4-dihydroxyphenyl)-2-aminoethanol 1-(3,4 -dihydroxyphenyl)-2-(methylamino)ethanol Methyl gallate 1.0% 1.0 98.0 100.0 1.0% 0.1 0.1 0.5 Ethyl alcohol 5.0 Purified water 93. 3% Total 100.0 (4) Oxidizing agent solution Hydrogen peroxide solution (30%) Stabilizer Purified water A hair dye is obtained by the same treatment as in Example 6.

Example 8 (1) Pretreatment liquid ammonium bisulfite solution (70%) γ-butyrolactone isopropyl alcohol urea betaine amphoteric surfactant (30%) 18.0% Appropriate amount 82.0 Total 100.0 Permanence of dark brown color 5 .0% 5.0 5.0 2.0 1.0 Purified water 72.0 Total 100.0 (2) Metal salt solution ferrous sulfate oleyl alcohol/ethylene oxide (20 mol) adduct 4.0% 1. 0 Purified water 95.0 Total 100.0 (3) Precursor solution Propyl gallate 0.5% Isopropyl gallate 0.5 Purpurogalin
0.11・2-dihydroxynaphthalene 0.05 Purified water
88.85 total 100.0 (4) Oxidizing agent solution Hydrogen peroxide solution (30%) Stabilizer purified water 15.0% Appropriate amount 85.0 100.0 Hair dye is obtained by the same treatment as in Example 6.

Example 9 (1) Pretreatment liquid, dark brown permanent ammonium bisulfite solution (70%) 15.0% Ethylene carbonate γ-valerolactone α-methyl-γ-butyrolactone Purified water 10.0 5.0 5. 0 65.0 100.0 (2) Metal salt solution glycine copper purified water 1.0% 99.0 100.0 (3) Precursor solution* Pyrocatechol 1.0% 6-hydroxydopamine 0.5 2 ・4・ 5 Entries Hydroxytolyl 0.1 3,4-dihydroxybenzoic acid 0.12,3-
Dihydroxybenzoic acid 0.1 Ammonia water (2
8%) Appropriate amount of purified water
98.2 Total 100.0 (4) Oxidizing agent liquid Hydrogen peroxide solution (30%) 18.0% Stabilizer Appropriate amount of purified water
82.0 Total 100.0 First, hair is treated with 80 gr of pretreatment liquid (1) for 10 minutes, and then washed with water.

Next, apply 80 gr of metal salt solution (2) to the hair for 10
After letting it stand for a minute, gently wipe off excess liquid.

Then, the precursor solution (3):oxidant solution (4) was mixed in a ratio of 4:1.
A permanent black hair dye is obtained by applying 80 gr of the mixed solution to the entire hair and leaving it for 15 minutes.

[Brief explanation of drawings]

Figure 1 shows the brightness (L value) of dyed hair, and the horizontal axis is Table 1.
The vertical axis shows the L value of the sample ivy. The smaller the L value, the higher the degree of staining. In the figure, the diagonal lines indicate samples that are examples of the present invention,
Those without diagonal lines are undyed white hair and exemplary samples outside the present invention. Figure 2 shows the hue and saturation (C-(a
2+b”)%) and is an example of the present invention.
5.6.7.8.9.10.11.12.13.14.
It can be seen that 15, 16, 17, 18 and 19) (black circles in the figure) are mostly concentrated at the origin, have low saturation, and are close to gray to black. Undyed white hair and samples other than those of the present invention (white circles in the figure) have high chroma, and the L value in FIG. 1 is also large.

Claims (1)

[Scope of Claims] 1. Sulfites or bisulfites or their effect promoting substances include ethylene carbonate, propylene carbonate, γ-butyrolactone, γ-valerolactone, δ-
Valerolactone, α-methyl γ-butyrolactone, β-
A pretreatment agent containing one or more of methyl-γ-butyrolactone and its derivatives, a metal salt solution containing a water-soluble salt of iron or copper, pyrocatechol, β-(3,4 dihydroxyphenyl) ) Alanine (dopa), dopamine, 6-hydroxydopamine, methyl 5,6 dihydroxyindole-2-carboxylate, 1-(3,4-dihydroxyphenyl)-2-aminoethanol, 1-(3,
4-dihydroxyphenyl L-1-(methylamino)ethanol, homocatechol, P-tert-butylcatechol, 3,4-dihydroxybenzaldehyde, 2.
3-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, caffeic acid, pyrogallol, gallic acid, methyl gallate, ethyl gallate, propyl gallate, isopropyl gallate, 2,4,5-trihydroxytoluene, 1・O- selected from the group of 2-dihydroxynafucrene, 2,3-dihydroxynafucrene, and flufrogalin
A precursor solution containing one or more hydroxy compounds with a molecular weight within the range of 110 to 220 selected from dihydroxy compounds or 5-hydroxyindoles that are monohydroxy compounds, and an oxidizing agent containing hydrogen peroxide. A hair dye consisting of liquid and solid liquid. 2. The hair dye according to claim 1, which is prepared so that the OPH value is 3 to 6 when the solid liquid of the pretreatment agent, metal salt solution, precursor solution, and oxidizing agent solution is mixed. 3 When the solid liquid of the pretreatment agent, metal salt solution, precursor solution, and oxidizing agent solution is mixed, the concentration of the hydroxy compound is 0.0.
The hair dye according to any one of claims 1 to 2, which is prepared to have a content of 5 to 0.2 mol/l. 4 When the solid liquid of pretreatment agent, metal salt solution, precursor solution, and oxidizing agent solution is mixed, hydrogen peroxide is 0.5 to 3% of the total amount.
．． The hair dye according to any one of claims 1 to 3, which is prepared to have a content of 0% by weight. 5. When the solid liquid of the pretreatment agent, metal salt solution, precursor solution, and oxidizing agent solution is mixed, the concentration of iron salt or copper salt is 0.01 to
The hair dye according to any one of claims 1 to 4, which is prepared to have a content of 1.0 mol/l.